Carboxylated starches as detergent builders

ABSTRACT

CERTAIN CARBOXY-CONTAINING DERIVATIVES OF STARCHES IN SALT FORM WITH AN AVERAGE OF MORE THAN CARBOXY GROUP PER REPEATING MONOMER UNIT, PARTICULARLY THOSE WITH MORE THAN ONE CARBOXYL GROUP PER REPEATING GLUCOSE UNIT ARE EXTREMELY EFFECTIVE DETERGENT BUILDERS IN BOTH SOLID AND LIQUID LAUNDRY DETERGENTS. DETERGENTS FORMULATED WITH THESE BUILDERS EXHIBIT EXCELLENT CHELATING ABILITY FOR HEAVY METAL IONS, AND EXCELLENT GENERAL DETERGENCY. THESE STARCH DERIVATIVE BUILDERS, UNLIKE THE COMMONLY USED PHOSPHATES AND NITRATES, DO NOT ACCELERATE EUTROPHICATION, SINCE THEY ARE NOT NOT ALGAE GROWTH STIMULANTS. ALKALI METAL SALTS OF CARBOXYMETHYL CELLULOSE ARE ALSO USEFUL IS BUILDERS.

United States Patent 3,629,121 CARBOXYLATED STARCHES AS DETERGENT BUILDERS Ibrahim A. Eldib, 22 Beekman Terrace, Summit, NJ. 07901 No Drawing. Continuation-impart of application Ser. No.

698,107, Jan. 16, 1968. This application Dec. 15, 1969,

Ser. No. 885,348

Int. Cl. Cllld 1/04 U.S. Cl. 252-89 17 Claims ABSTRACT OF THE DISCLOSURE Certain carboxy-containing derivatives of starches in salt formwith an average of more than one carboxy group per repeating monomer unit, particularly those with more than one carboxyl group per repeating glucose unit are extremely effective detergent builders in both solid and liquid laundry detergents. Detergents formulated with these builders exhibit excellent 'chelating ability for heavy metal ions, and excellent general detergency. These starch derivative builders, unlike the commonly used phosphates and nitrates, do not accelerate eutrophication, since they are not algae growth stimulants. Alkali metal salts of carboxymethyl cellulose are also useful is builders.

CROSS REFERENCES This application is a continuation-in-part of Ser. No. 698,107 entitled Polyacrylates of Selective Viscosity as Detergent Builders filed Jan. 16, 1968 and still pending.

BACKGROUND OF THE INVENTION It is known that some materials improve the detergency levels of soaps and synthetic detergents and these are commonly used in detergent compositions. Such cleaning boosters are called builders. Builders permit the attainment of superior cleaning performance, both as regards cost and quality of finished work, than is possible when so-called unbuilt compositions are used.

The behavior and mechanism by which builders perform their function is not fully understood although several explanations for their behavior are available. Unfortunately, an unequivocal criterion does not exist which would permit one to predict accurately which class of compounds possess valuable builder properties and which compounds do not.

This may be explained in part by the complex nature of detergency and the countless factors which contribute to overall performance results. Builder compounds have been found to have some effect, for instance, in such areas as stabilization of solid soil suspensions, emulsification of soil particles, solubilization of water-insoluble materials, foaming of washing solutions, peptization of soil agglomerates, neutralization of acid soil, and the inactivation of mineral constituents present in the washing solution. Thus, any theoretical discussion of the detergent boosting capacity of a builder compound must take into account all the significant individual actions involved in the detergent process and all usual conditions of soiling and washing.

[Examples of known inorganic builder materials include: water-soluble inorganic alkaline builder salts which can be used alone or in combination, including alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates.

Examples of known organic builder materials include: alkali metal, ammonium or substituted ammonium aminopolycarboxylates, e.g. sodium and potassium ethylenediaminetetraacetate, sodium and potassium and triethanolammonium N (Z-hydroxyethyl)-nitrilodiacetate. Alkali metal salts of phytic acid, e.g. sodium phyta-te, are also suitable as organic builders.

Very significantly, there is currently a greatly increased pressure from the Federal Government to eliminate algae growth caused by nitrogen and/ or phosphorous containing compounds. Most of the common builders contain one or both of these elements.

The ever increasing interest in built detergent compositions has resulted in an expanding list of available builder compounds. Despite the length of this list, however, certain disadvantages and shortcomings in addition to algae growth, are recognized in known builder compounds.

Perhaps .the most widely acknowledged limitation is in connection with the series of condensed inorganic polyphosphate compounds such as alkali metal tripolyphosphates, and higher condensed phosphates. These compounds, which constitute the most widely commercially used builders when used in detergent compositions have a strong tendency to hydrolyze into less condensed phosphorous compounds which are relatively inferior builders and, which may, in fact, form undesirable precipitates in aqueous washing solutions. Such lower forms include orthophosphate.

Special attention must be given to the terminology used with detergent formulations which are useful in dishwashing and laundering compositions. The applications for which these compositions are used are generally referred to by such terms as light-duty and heavyduty. These terms as applied to detergency have acquired fairly definite meanings in the art.

Light-duty applications are those such as the handwashing of dishes and lightly soiled fine fabrics, which fabrics cannot as a rule withstand the vigorous treatment of machine laundering. Also, light-duty washing situations are those which generally call for a gentle washing action in cool or lukewarm water. It is well-known by those skilled in the art that compositions designed for such uses must have certain performance properties which distinguish them from heavy-duty cleaning compositions. For instance, they must be mild to the skin, possess high sudsing properties, and also possess cleaning power in water solutions having cool or lukewarm tomperatures, e.g., below F.

The term heavy-duty applications refers to those cleaning situations in which heavily soiled articles are encountered. Considerations in such cleaning processes include the use of vigorous mechanical action, usually in hot Water having temperatures between about F. and up to about 200 F. Moreover, the problems presented by high soil loads or fabrics such as cotton are unlike those dealt with in light-duty situations. As a result, heavy-duty detergent compositions must be separately and specially formulated. These heavy-duty detergents are often used by housewives for light duty applications.

In the formulations of heavy-duty built detergent laundering compositions, the most valuabie detergents are those which combine effective cleaning ability with superior whiteness maintenance results. Cleaning pertains to the removal of soil from solid articles. Whiteness maintenance is a term which is used to measurethe ability of an aqueous solution, of a detergent composition to keep suspended in the solution, soil which has been removed during the washing process.

The detergent formulations prepared from builders can not only be generally classified as light-duty and heavy-duty but can be prepared in several different physical forms. These include granular, flake, liquid and tablet forms or more generally, liquid and solid forms.

The behavior and efiicaciousness of builders will vary greatly from builder to builder. Furthermore, a specific builder often will not be effective in all types or physical forms of detergent formulations. For instance, a builder that is suitable for a heavy-duty solid detergent may be unsuitable for a heavy-duty liquid. If suitable in a heavyduty liquid, it may be entirely unsuitable in a solid. Thus, there is virtually no predictability in builder behavior even within the general class of detergent compositions.

BRIEF SUMMARY OF THE INVENTION It has been discovered and forms the substance of this invention that certain carboxy-substituted starch derivatives i.e. starch polyelectrolytes and/or their salts impart surprisingly outstanding building power to detergent formulations, particularly heavy duty ones, while at the same time are incapable of algae stimulation, contrary to the commonly used phosphate builders. The alkali metal salts of Carboxymethyl cellulose which are soil suspending agents can also be used as builders if used in much larger quantities than is normal for antisoil depositing agents.

DETAILED DESCRIPTION WITH PREFERRED EMBODIMENTS The especially preferred starch derivative species for the purpose of this invention are certain carboxymethyl starches and starch dicarboxylic acids. Carboxymethyl starch has generally been prepared by the reaction of an alkali and an etherifying agent with the starch. A major difficulty with this process had been due to the tendency of starches to form semi-solid gels when treated with alkali. The gel formation prevents a uniform reaction of the alkali starch with the etherifying agent unless the alkali-treated material is very dilute or is first subjected to a thorough grinding operation, and even then a prolonged period is required for satisfactory etherification. The product finally obtained by this procedure is a coarse solid, difiicult to purify unless milled or dissolved in water and reprecipitated with the aid of a miscible organic agent such as methanol.

The preferred present method (US. Pat. No. 2,599,- 620) preferably uses monochloroacetic acid as an etherifying agent; the finely divided starch can be used directly, the alkali is introduced in the form of an aqueous solution and water can be introduced with the etherifying agent. An alcohol is used as a medium of reaction to overcome the difiiculty obtained in the previous procedure. Good results can be obtained by using an alcohol of the lower aliphatic group. In carrying out the reaction it is preferred to operate at a temperature near the boiling point of the alcohol, although highly satisfactory results can be obtained at temperatures as low as 50 C. with a longer duration.

The preferred process illustrated with chemical formulas is as follows for preparing carboxy methyl starches.

(IJHZOII H E O H Alcohal g NaOH I I H OCHQCOONZI n Sodium salt of (-arhoxyuwthyl starch. Degree of substitution in this formula is 3.0

The Carboxymethyl starch illustrated by the formula above on the right is a polymeric material with numerous repeating units of the nature set forth above usually it will have a value of from 1,000 to 5,000, preferably 2,000 to 4,000 and most preferably 2500 to 3500.

The simple unit shown above does not give a complete picture of the amount of variation the complete structure may contain. Thus, there can be a variety of structures (some including phosphate linkages between anhydro glucose units) depending on the parent from which the carboxymethyl starch has been derived.

The various parent starches (e.g. corn, potato, wheat, tapioca, barley, sage, flour, rice, etc.) will all contain the characteristic anhydroglucose unit. But each parent starch will have different degrees of branching instead of a linear chain structure.

Carboxymethyl cellulose has a repeating unit of ([JInoomoooNa 1? TH 011 H H H H o l l it on oHgoorncooNa As regards the location of carboxymethyl groups in each ring unit, surprisingly, the carboxymethyl cellulose is considerably different in detergent behavior as compared to the carboxymethyl starches.

.Starch dicarboxylic acids (salt form) having about 45% by weight of carboxyl content have been found to possess the highest calcium sequesteration ability among all the starch polyelectrolytes and were the best detergent builders of all the oxidized starches in solid laundry detergents. Generally, the starch dicarboxylic acids will have a carboxylic acid content of about 15 to 47%, preferably 20 to 47%, most preferably 22 to 47%. They are as good in detergency as the commonly used phosphate-containing builders. Polyphosphates used in solid laundry detergents constitute the biggest portion (45 of the total detergent phosphate market.

But, surprisingly, the starch dicarboxylic acids, while effective as builders in liquid laundry detergents, are not as good as tetrapotassium pyrophosphate, (TKPP).

One reason that starch dicarboxylic acids may be especially effective in solid formulations is that there appears to be a synergism between them and sodium sulfate. Sodium sulfate is not used in liquid formulations.

Starch dialdehydes and closed ring oxidized starches are poor sequesterants and also not suitable as builders.

Carboxymethyl starch of a certain branched chain structure and a minimum percent carboxy group content of from 10 to 40.2, preferably 15 to 40.2 and most preferably 15 to 30, performed better than TKPP in liquid laundry detergents and approximately equivalent to sodium tripolyphosphate (STPP) in solid laundry detergents.

Generally, satisfactory carboxymethyl starches have a carboxy degree of substitution of about .5-2.5, preferably 1-1.5 and most preferably 1.2-1.5. Starch derivatives obtained from starches made from granular (nonsolution) reactions and staining blue with iodine will probably not be good detergent builders. However, these derivatives can be mildly degraded to produce effective detergent builders. Degradation can be effected in a variety of conventional techniques, such as autoclaving, acid hydrolysis. Enzymatic reactions can also be used to degrade the derivative.

Carboxymethyl starch derivatives of very high molecular weight which are obtained by any process can be improved for builder purposes by employing the same degradation technique as described above. The satisfactory carboxymethyl materials will have been derived from a solution process and will not show a blue stain from iodine.

Generally, the molecular weight of satisfactory carboxy methyl starch and dicarboxylic acid starch builders will range between 200,000 to 1,000,000, preferably 500,000 to 800,000, and most preferably about 700,000 to 800,000 weight average molecular weight.

In general, there are two other approaches which can be used to form carboxy containing starches through oxidation. One of these is closed ring oxidation, the other open ring oxidation.

Thus, oxidation can be sufiiciently mild such that the primary alcohol attached to the fifth carbon is converted into a carboxyl group, or it can be strong enough to break the bond between the second and third'carbon atoms and convert the alcohol groups to the aldehyde groups. The aldehyde groups are then subsequently oxidized to carboxyl groups.

In closed ring oxidation, the reaction is carried out by treating an aqueous starch suspension with a slightly alkaline solution of sodium hypochlorite. The oxidation is affected by reduction of the negative valent chlorine with the subsequent release of oxygen.

The primary alcohol attached to the fifth carbon is converted into a carboxyl group along with the formation of water. The oxygen not consumed in the formation of carboxyl groups probably assists in the depolymerization of the starch chains through oxidative alkaline degradatioin. This results in lower paste viscosities.

Since reaction time, temperature and pH can be varied, a series of progressively higher fiuidities may be manufactured. The greater the oxidation of a starch, the higher is its fluidity. When laboratory control indicates that the desired fluidity has been reached, a calculated amount of anti-chlor (sodium bisulfite) is added to stop the oxidation. The pH is then adjusted and the starch is repeatedly washed to remove excess salts, filtered and dried to an average moisture content of 12%.

Closed ring oxidized starch retains the granule structure of unmodified starch, shows typical polarization crosses, is insoluble in cold water, and shows the typical starch iodine reaction.

Oxidized starches prepared from the closed ring reaction are available from several producers.

The first report of a promising experimental open ring oxidation of corn starch by periodic acid is that of J ack- I L H OH Starch Unit Dialdehyde Unit Since the consumption of H10 proceeds at a greatly diminished rate after the consumption of one mole of oxidizing agent, it is apparent that the principal reaction is completed at this stage.

Miles Laboratories make a dialdehyde starch known commercially as DASOLA. This dialdehyde prepared from corn starch can contain from 5-100% of dialdehyde units. This dialdehyde starch can be converted into opened ring dicarboxyl starches by the chlorous acid oxidation of periodate oxidized starches (see US.

2,894,945). The reactions take place in aqueous acid medium and the products are isolated in good yield by precipitation with alcohol. The reaction is illustrated as follows:

Dialdehyde Unit Dicarboxylic Acid *n is a number from 1,000 to 5,000 preferably 2,000 to 4,000 and most preferably 2,500 to 3,500.

No commercial quantities of starch dicarboxylic acids are available on the market at this time.

While the above formula for dicarboxylic acid is applicable to at least some of the repeating units in the backbone, it was found that the oxidation process can be controlled such that either all the dialdehyde groups are converted to carboxylic groups or that only a portion of them is converted as shown below:

sarily result in a clear solution (two phases or a precipitate are possible). The difference between chelation and Starch is an extremely widely available material since almost every plant has large quantities of it, for instance, wheat is about 54 to 58 wt. percent starch and corn is 55 to 65 wt. percent starch. The extraction and recovery processes to obtain starch from their raw materials is an extremely well-known process to the art and need not be detailed here.

Starch is a high molecular-weight polymer of D-glucose and is the principal reserve carbohydrate in plants. Most starches consist of a mixture of two types of polymers, namely amylose and amylopectin. Significant differences in the chemical nature and physical properties exist between the two types of polymers while minor differences may exist in the properties of preparations of the same starch from different plant sources.

The proportion of amylose and amylopectin varies in different starches but is generally in the range of one part of amylose and three parts of amylopectin.

The linear polymer of starch has been designated as amylose or the A-fraction. In this polymer the glucose units are joined by aD(l- 4) linkages to yield linear chains of several hundred glucose units.

The branched polymer of starch has been designated as amylopectin or the B-fraction. The molecular size of amylopectin ranges from several hundred thousands of D glucose units per molecule. The types of linkages that have been definitely established in amylopectin are the aD(l- 4) and the u-D(l 6). The latter linkages give rise to the so-called branch points in the mole cule.

In formulating a detergent, many compounds are used. Frequently, these compounds are not supplied in 100% active form. Thus, the formulator must know the actual percentage of the active ingredients in each component. Furthermore, the formulator must clearly understand the basis on which the percentage of the active ingredients is reported.

Percent activity of oxidized starches, starch dicarboxylic acids, carboxymethyl starch was measured for the purposes of this application as weight percent carboxyl content, because the carboxyl groups play the main role in chelating heavy metal ions. High carboxyl content in a compound indicates a potential for good detergency building power.

From the foregoing structural formulae and by computing molecular weights, it can be calculated that ring oxidized starch has maximum carboxyl content of 25.57% when every alcohol group in position on the ring has been oxidized to the carboxylic acid group.

Starch dicarboxylic acid is formed in a sequence of reactions which have been shown above and can have a maximum carboxyl content of 47.1% when the alcohol group in positions 2 and 3 on the ring have been oxidized to the carboxylic acid group. Of course, the carboxyl acid content can be below the maximum because of the considerations previously discussed.

Carboxymethyl starch will have a maximum, by weight, of about 40.2%-COOH groups and sodium carboxymethyl starch will have a maximum of about 50.0% COONa content by weight when all three alcohol groups on positions 2, 3 and 5 have been carboxymethylated in each monomer unit.

Chelating agents are a special class of complexing agents which react with a wide variety of metal ions to form especially stable, metal, complexes, chemically bonded in a ring structure. The chelation does not necessequestration is that a ring structure need not be present in sequestration (sequestration will always result in clear solution).

When both chelation and sequestration occur, the result is a ring compound held in solution which ties up the polyvalent ions so that they are not free to react with other components (such as surfactants) also present in the water.

It is believed that S-membered rings (including the cation, i.e. calcium) are required before a stable complex can be formed. The starch complex structure of the carboxylic acid derivatives has a ring structure suitable for chelation.

The water soluble salts of the starch derivatives described above to useful detergent builders are especially preferred for the purposes of the invention. The watersoluble salt can be alkali metal or ammonium or substituted ammonium salt. The alkali metal can be sodium or potassium. The salt can be used in a partially or fully neutralized form. Also partial neutralization and esterification of the acid groups can be carried out while still retaining the effective properties of the homopolymer.

Starch derivatives are converted to the desired salt by reacting with the appropriate base, generally with a stoichiometric excess of the desired percent of conversion. Normally 100% of the carboxy group will be converted to its equivalent salt, but the percentage can be less in certain situations.

As will be seen in the examples following, the carboxy starches of the invention are particularly outstanding in terms of their ability to chelate calcium ions. This allows it to serve the important function of chelating calcium so that the water in which the detergent is operating is softened. Generally, a minimum chelation ability of at least mg. CaCO /gram of builder is preferred for a solid detergent and a minimum of about 35 for a liquid detergent.

Three of the starch dicarboxylic acids had the highest sequestration power for calcium among all starch derivatives evaluated. The sequestration power of these starch dicarboxylic acids is superior to that of tetrapotassium pyrophosphate (TKPP) which is used in liquid household laundry detergents. The chelation sequestration power of the preferred carboxymethyl starches of the invention is inferior to STPP but superior to TKPP. Closed ring oxidized starches are very poor sequesterants.

In the examples, the concentrations of builder used and chelation-sequestration evaluations were based on the concentration of carboxyl units rather than on the concentrations of the mixture of converted and unconverted starch. Using this basis, the concentration of the converted groups will be a constant at any given builder concentration.

Generally, washing performance is at a maximum at a high level of alkalinity. The commercially used phosphate builders are buffers as well as chelating agents. A further advantage of the carboxy starch derivatives of the invention is that there is unexpectedly only a very small loss of alkalinity in the wash solution and this can be easily remedied with small amounts of standards builders such as STPP or TKPP.

An additional advantage of the carboxy starch derivatives of the invention is that they are stable to hydrolysis while polyphosphates as mentioned above can be converted into inferior reaction products by hydrolysis.

In general, in the detergent compositions of this in-" vention, the essential ingredients are (a) an organic water soluble detergent surface active material as defined and illustrated below and (b) the carboxy starch builder compound meeting the requirements specified and exemplified herein.

The detergent compositions of this invention, therefore, contain the essential ingredients in a ratio of carboxy starch builder to detergent surfactant in the range of about 1:5 to about 10:1 by weight, with such compositions providing in aqueous solution a pH of about 9 to about 12. The preferred ratio of carboxy starch builder to detergent surfactant is about 1:2 to about 5 :1 and the optimum pH range is 9.5 to about 11.5.

The detergent surface active compounds which can be used within the compositions of this invention include anionic, nonionic, zwitterionic, ampholytic detergent compounds and mixtures thereof. These suitable substances are outlined at length below:

(a) Anionic detergent compositions which can be used in the compositions of this invention include both soap and non-soap detergent compounds. Examples of suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C C Particularly useful are the sodium or potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap, tall oils and SAS (sodium alkane sulfonates). Examples of anionic organic non-soap detergent compounds are the water soluble salts, alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the synthetic detergents which form a part of the compositions of the present invention are the sodium or potassium alkyl sulfates especially those obtained by sulfating the higher alcohols (C C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl ben- Zenesulfonates, such as are described in US. Letters Pats. No. 2,220,009 and No. 2,477,383 in which the alkyl group contains from about 9 to about 15 carbon atoms; other examples of alkali metal alkylbenzene sulfonates are those in which the alkyl radical is a straight or branched chain aliphatic radical containing from about 10 to about 20 carbon atoms for instance, in the straight chain variety 2-phenyl-dodecanesulfonate and 3-phenyl-dodecane-sulfonate; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g. tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium or potassium salts or alkylphenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain about 9 to about 12 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl tauride in which the fatty acids, for example, are derived from coconut oil; and others known in the art.

(b) Nonionic synthetic detergents may be broadly defined as compounds aliphatic or alkylaromatic in nature which do not ionize in water solution. For example, a well-known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with an hydrophobic base formed by condensing ethylene oxide with an hydrophobic base formed by the condensation of propylene oxide with propylene glycol.

The hydrophobic portion of the molecule which, of course, exhibits water insolubility, has a molecular weight of from about 1,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

(1) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.

(2) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene-diamine. For example, compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said hydrophobic bases having a molecular weight of the order of 2,500 to 3,000, are satisfactory.

(3) The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

(4) Long chain tertiary amine oxides corresponding to the following general formula, R R R N O, wherein R is an alkyl radical of from about 8 to 18 carbon atoms, and R and R are each methyl or ethyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyl-dodecylamine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide.

Long chain tertiary phosphine oxides corresponding to the following formula RRR'P -O, wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semipolar bond. Examples of suitable phosphine oxides are:

dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, bis(hydroxymethyl) dodecylphosphine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide, 2-hydroxypropylmethyltetradecylphosph'ine oxide, dimethyloleylphosphine oxide, and dimethyl-2-hydroxydodecylphosphine oxide.

(6) Dialkyl sulfoxides corresponding to the following formula, RRS 0, wherein R is an alkyl, alkenyl, betaor gamma-monohydroxyalkyl radical or an alkyl or betaor gamma-monohydroxyalkyl radical containing one or two oxygen atoms in the chain, the R groups ranging from 10 to 18 carbon atoms in chain length, and wherein R is methyl or ethyl. Examples of suitable sulfoxide compounds are:

dodecylmethylsulfoxide tetradecylmethylsulfoxide 3-hydroxytridecyl methyl sulfoxide 2-hydroxydodecyl methyl sulfoxide 3-hydroxy-4-decybutyl methyl sulfoxide 3-hydroxy-4-dodecoxybutyl methyl sulfoxide 2-hydroxy-3-decoxypropyl methyl sulfoxide 2-hydroxy-3-dodecoxypropyl methyl sulfoxide dodecyl ethyl sulfoxide 2-hydroxydodecylethylsulfoxide The 3-hydroxy-4-decoxybutyl methyl sulfoxide has been found to be an especially effective detergent surfactant. An outstanding detergent composition contains this sulfoxide compound in combination with the carboxy starch builder compounds of this invention.

Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium- 3-dodecylaminopropanesulfonate.

(d) Zwitterionic synthetic detergent surfactants can be broadly described as derivatives of aliphatic quaternary ammonium compounds in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group. Examples of compounds falling within this definition are 3-(N,N dimethyl-N-hexadecylammonio)propane-l-sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropanel-sulfonate which are especially preferred for their excellent cool water detergency characteristics.

The anionic, nonionic, ampholytic and zwitterionic detergent surfactants mentioned above can be used singly or in combination in the practice of the present invention. The above examples are merely specific illustrations of the numerous detergents which can find application within the scope of this invention.

A granular detergent composition can contain a carboxy starch builder of this invention and a detergent surfactant in the weight ratio of about 121.5 to about 10: l. The preferred ratio of builder to surfactant is about 1:2 to about :1. Another embodiment of this invention is a built liquid detergent composition containing a carboxy starch builder described above and a detergent surfactant in a weight ratio of builder to detergent of about 1:1.5 to about :1. The preferred ratio for built liquid compositions of carboxy starch builder to detergent is about 1:2 to about 3:1.

The detergent compositions described by this invention employing a carboxy methyl starch builder compound as defined above also have special applicability in the area of heavy duty built liquid detergents. This area presents special problems to the formulator in view of the peculiarities inherent in aqueous systems and the special requirements of solubility of the ingredients and, more especially their stability in such mediums.

It is well known, for instance, that sodium tripolyphosphate, while outstanding in its behavior in granular compositions, is generally regarded as being unsuited for built liquid detergents, because of its propensity to hydrolyze into lower forms of phosphates. Thus, as a practical consideration there has been a necessity of resorting to alkali metal pyrophosphates, such as K4P20'], in Order to prepare a built liquid detergent. This has been true notwithstanding the known inferiority of pyrophosphates to sodium tripolyphosphate in some compositions, for example, as a builder for heavy duty detergency.

In view of the increasing acceptance by the general public of built liquid detergents for dishwashing, it is very significant and a featured contribution of this invention that an improved liquid detergent product is now possible that will provide detergent levels superior to a tetrapotassium pyrophosphate built liquid product without the troublesome stability problem presented by sodium tripolyphosphate.

Most of the built liquid detergents commercially available at the present time are either water based or have a mixture of water and alcohol as the liquid vehicle. Such vehicles can be employed in formulated built liquid detergent compositions according to this invention Without fear of encountering stability problems. Accordingly, a built detergent composition of this invention can consist essentially of a carboxy methyl starch builder as defined herein and an organic detergent surfactant in the ratios described above and the balance being a vehicle medium, for example, water, a water-alcohol mixture, liquid nonionic surfactant compounds, etc.

An additional advantage of this invention is that hydrotropes are not necessary in these heavy duty liquid detergents and therefore a more effective concentrated formulation can be prepared than previously possible.

In a finished detergent formulation of this invention there will often be added in minor amounts materials which make the product more effective or more attractive. The following are mentioned by way of example. Soluble sodium carboxymethylcellulose (CMC) can be added in minor amounts to inhibit soil redeposition although in most instances the carboxy starch derivative itself will perform as a soil redeposition inhibitor. When carboxymethylcellulose (sodium form) is used as a builder it also performs the function of an anti-soil redeposition agent.

A tarnish inhibitor such as benzotriazole or ethylenethiourea can also be added in amounts up to about 2%.

An alkaline material or alkali such as sodium hydroxide or potassium hydroxide can be added in minor amounts as supplementary pH adjusters.

There might also be mentioned as suitable additives, water, brightening agents, bleaching agents, sodium sulfate, and sodium carbonate.

Corrosion inhibitors can be added. Soluble silicates are highly effective inhibitors and can be added to certain formulas of this invention at levels of from about 3% to about 8%.

Alkali metal, preferably potassium or sodium, silicates having a weight ratio of SiO :M O of from 1:1 to 2.8:1 can be used. M in this ratio refers to sodium or potassium. A sodium silicate having a ratio of SiO :Na O of about 1.6:1 to 2.45:1 is especially preferred for economy and effectiveness.

When washing at temperatures in the range of 170l90 F. such as being practiced in Europe perborate salts can be incorporated in the cleaning and laundering formulations claimed in the invention. Perborates are bleaching agents which release oxygen in water at high washing temperatures. A heavy duty powder detergent containing 15% starch polyepectroly (carboxylates). 15% sodium perborate 15% LAS, 10% NaCMC and 5% sodium silicate sodium sulfate and the balance moisture is recommended for Europe.

While a hydrotrope will not ordinarily be found necessary, it can be added if so desired. Suitable hydrotropes are water soluble alkali metal salts of toluene-sulfonate, benzenesulfonate, citric acid and xylenesulfonate. The preferred hydrotropes are the potassium or sodium toluenesulfonates. The hydrotrope salt may be added if so desired, at levels of 0% to about 12%.

The specific action of the carboxy starch builders of this invention will vary to some extent, of course, depending upon the ratio of active detergent to builder mixture in any given detergent composition. There will be considerable variation in the strengths of the washing solutions employed by diflFerent users, i.e., some users may tend to use less or more of the detergent compositions than will others. Moreover, there will be variations in temperature and in soil loads as between ditferent washing operations. Further, the degree of hardness of the water used to make up the washing solutions will also bring about apparent diiferences in the cleaning power and whiteness maintenance results. Finally, different fabrics will respond in somewhat different ways to different detergent compositions. The best type of detergent composition is one which accomplishes an excellent cleaning and whiteness maintenance eifect under the most diverse cleaning conditions. The built detergent compositions of this invention are valuable in this respect.

It has been additionally discovered that water soluble alkali metaland ammonium (including substituted ammonium) salts of citric acid have been found to be extremely eifective builders. They can be used in heavy duty solid detergents, heavy duty liquid detergents, medium duty solid detergents and light duty liquid detergents. Citrates are particularly good cleaners in the latter three and outstanding in light duty liquids. They can be formulated into detergent formulations according to the above disclosure.

Citrates also have an important advantage in detergent formulations that come into contact with the skin, since they do not cause skin irritation.

Additionally, it has been unexpectedly discovered that salts of copolymers of ethylene and maleic acid are also good detergent builders. Generally, there will be at least 20 mole percent of maleic acid in the polymer. It follows that copolymers of other unsaturated dicarboxylic acids with ethylene and other olefins can also be used for this purpose.

The invention is further illustrated by the following examples. All starches used in these examples were the sodium salt form unless otherwise indicated.

EXAMPLE 1 As has been detailed above the ability of a detergent builder to either chelate or sequestrate or both is a key characteristic. Accordingly, the chelation-sesquestr-ation value of various starches, starch derivatives and cellulose derivatives were determined and compared to standard phosphate builders. The procedure used was as follows:

An amount equivalent to two grams of pure chelant material capable of chelation or sequestration was accurately weighed and dissolved in ml. of distilled water. 10 mls. of 2% sodium oxalate indicator was added. The solution was then diluted to 250 mls. The pH was adjusted to the appropriate value using 10% sodium hydroxide. The solution was then heated to 140 F. (in order to simulate actual washing conditions). A small sample was withdrawn and used to adjust the spectrophotometer to 100% transmission at 550 mM. The sample was then returned to the solution being titrated. At this point 2 mls. or smaller increments of titrant solution (calcium acetate) were added.

Samples were withdrawn periodically and percent transmission taken; samples were then returned to the solution being titrated. During each cycle, the pH was adjusted before the sample was removed to restore it to its initial pH. Equilibration was controlled with continuous agitation. The cycles were repeated until permanent and noticeable turbidity was observed. This was well past the endpoint. A plot of milliliters of CaAC added against percent transmission at 550 mM shows a sudden break at the end point. This enables percent calculation of end point.

Constant pH was maintained by continuously monitoring pH during the titration and adding small quantities of very dilute sodium hydroxide as the titration proceeded.

Chelation value was calculated using the following formula:

(ml. calcium acetate) X25 milligrams CaCO chelated sample Weight, grams per gram of Chelating agent The results are summarized in Tables I and II following.

EL TI E UESTRATION POWER OF STARCH DERIVATIVES (GRANULAR)* EVALUATED AS CHELATING TABLEI CH A ON S Q AGENTS FOR USE AS DETERGENT BUILDERS Degree of Percent substi- Chelation carboxyl tution value, mgs. Type of starch derivative Parent starch groups 2 (actual) Caco /grn.

Carboxymethyl starch Corn 26. 8 2 47, 5 25% straight amylose; branched d 40. 2 3 22. 25 Carboxymethyl starch, 25% straight; 75% branchedufl 40. 2 3. 0 22. 25 Carboxylmethyl starch, branched amylopectin Waxy corn starclL. 26.8 2 44. 37 Oarboxylmethyl starch high amylose content, 55% straight; 45% branched Corn 40. 2 3 10, 0 Carboxymethyl high fluidity starch-acid hydrolyzed to lower v1sc0s1ty, 55% straight; 45% do 40 2 3 2 25 branched Oarboxymethyl starch high amylase-not acid modified, 55% straight; 45% branched d0 40. 2 3 24. 4 Carboxymethyl starch, 100% branched Waxy corn starch 40. 2 3 23 8 High viscosity carboxyrnethyl starch. Corn 3. 4-5. 4 0. 25-0. 4 0 Low viscosity carboxymethyl starch 3. 4-5. 4 0. 25-0. 4 0 Sulfonated carboxymethyl starch 3. 4 0. 25 0 Carboxymcthyl starch 3. 4 0. 25 0 D0 3. 4 0. 25 0 Carboxymethyl cellulose from City Chemical 9. 4 0.7 15. 1

1 Prepared by the granular method.- 2 As acid form unless specified.

TABLE II.CHELATION-SEQUESTRATION POWER OF STARCH DERIVA- TIVES (OXIDIZED) EVALUATED AS CHELATING AGENTS FOR USE AS DETERGENT BUILDERS 1 Obtained from National Starch & Chemical Corporation.

2 100% conversion to aldehyde group.

3 Based on 100% active material.

4 Sample actually contained 14.53% moisture, giving a true percent activity of 85.47.

As can be seen from the preceding Tables I and II:

1) Starch dicarboxylic acids have the highest chelation power among all the materials tested. However, carboxy methyl starches show good chelating values. For instance, a carboxy methyl starch having 25% straight amylose and 75% branching and 26.8% carboxylic groups shows a chelating power somewhat greater than T KPP.

(2) Carboxy methyl starches of no branching and low carboxy content are not good chelating agents.

(3) Oxidized starches and starch dialdehydes performed very poorly in chelation evaluation. In effect, these structures will not chelate divalent metal ions.

(4) Carboxy methyl cellulose has borderline chelation properties.

(5) Later examples will further illustrate that the The cotton detergency tests were carried out according to the following procedure:

Laundry detergents (heavy duty solid in this example) were tested in a commercial testing apparatus made by the US. Testing Co. called the Terg-O-Tometer in order to measure the soil removal from the cotton fabric. The Terg-O-Tometer consists of four pots which can be operated simultaneously. Operating conditions can be varied, e.g., temperature, agitation speed and duration of washing or rinsing.

Standard soiled cloths are available from a number of sources. In these tests, except those shown in Tables IV and V, Forster D. Snell (F.D.S.) soiled cotton was employed. Before sailing it had an initial reflectance of 18.5 :2.0%.

synthesis of the starch derivative i.e. solution or granular 5 The procedure is to cut the cloth into swatches of 3 /2 has a strong influence on the derivatives capabilities as a by 4 inches. Four of these swatches are then placed in builder. each pot.

The chelation power of these carboxymetyl starches The pots have previously been charged with one liter and starch dicarboxylic acids is superior to that of tetraof water and a specified quantity of detergent (2.0 gram), potassium pyrophosphate presently used in liquid houseand the agitators have been operating for a one minute hold laundry detergents. period. The solution is already at the desired temperature,

The chelation-sequestration power of starch disarbo- 140 F. The swatches are then washed for exactly 10 xylic acids is less than sodium tripolyphosphate but as minutes. At the conclusion of this period, the pots are relater examples will illustrate the starch dicarboxylic acids moved, the solutions discarded, and the swatches wrung are at least equal to STPP builders in solid detergents. out by hand. The swatches are then returned to the pots Oxidized starches performed very poorly as chelants. which now contain one liter of water and (the swatches) These materials cannot be used as detergent builders. are then rinsed. This rinsing lasts five minutes, after which Those which have a chelation ability greater than 40 the entire rinsing procedure is repeated. In both the washmgm. CaCO per gm. of material should act as good ing and rinsing procedure, the water employed is disbuilders, particularly inliquids. tilled water doped with calcium salts in an amount equi- Thus, it is apparent that there is a correlation between valent to 120 p.p.m. of calcium carbonate, which simuchelation value and builder performance. However, belates hardness. yond a certain chelation value, i.e. about 100, improve- At the end of the second rinsing, the swatches are ironed ment in builder performance drops to almost zero. dfiy. Great care must be taken in order to avoid scorching t e swatches. EXAMPLE 2 Once dried, reflectance measurements of the swatches A series of heavy duty solid detergents were formulated by a photovolt refiectometer with a search unit containing to be used in the cotton detergency tests of this example. a green tristimulus filter is carried out. The refiectometer The formulations used were of the following type with No. 610 employed is manufactured by Photovolt Corporaonly the builders being different from formulation to tion. The refiectometer is adjusted so that soiled cotton formulation. gives a reading of zero on the scale, while unsoiled cotton f 100. The readin from the washed Heavy duty solid formation Percent by wt. glves a leading g Surfactant linear alkyl C13 (average) benzene szvnagcllghus is directly related to the percentage of soil g All results reported are statistical averages. Each data ""1". point is the average of not less than 4 nor more than 20 Sodium meta silicate 5 mdividual tests.

335 6- 1 -g The data obtained are illustrated in Table III as follows: In this Table III the weight percent of builder represents ZEZL i'gg 40 builder in the washing solution which corresponds to TABLE III.-DETERGENCY BUILDING POWER OF CARBOXYME'IIIYL AND DICARBOXY STARCHES FROM VARIOUS SOURCES AND CARBOXYMETI'IYL CELLULOSE IN HEAVY DUTY SOLID LAUNDRY DETERGENT FORMULATIONS Percent reflectance at different builder concentrations Iercent carboX- 0.019 0.02 7 0.03 7 0.067 0.097 5.12 M t naltogtod ylation buildei builde? builder buildei buildei buildzi Carboxylncthyl starch l Carboxymethyl starch, 25% straight amylose; 75% branc ed (Jarboxymcthyl starch, 100% branched amylopcctin corn Carboxymcthyl starch, 55% straight; branched corn Uarboxymethyl starch high fluidity-acid hydrolyzed to lower viscosity,

straight; 45% branched Carboxymethyl starch high amylose not acid modified, 55% straight; 45%

branched Starch dicarboxylic acid F Srarch diearbocylic acid G Carboxymcthyl starch 100% branched Carboxynlethyl starch hi-amylose content (larboxyrnethyl starch hi-amylose content. lligh viscosity carboxymethyl starch Low viscosity carboxyntethyl starch Sulionatcd enrboxymcthyl starch. Carboxymethyl starch Do Carboxymethyl cellulose Carboxymethyl starch, 25% straight; branched 1 From National Starch and Chemical Corporation (1.34 degrees of substitution).

/s X10 weight percent builder in the detergent formulation prepared. Thus, 0.06% builder corresponds to 30% builder in the detergent compound while 0.01% builder corresponds to builder in the detergent compounds. The total detergent (all compounds together) concentration was the same in all washing experiments and was 0.2% of the wash solution.

As can be seen from the preceding Table III the carboxymethyl starch with 18% degree of carboxylic acid content showed outstanding detergency in a heavy duty solid detergent.

Furthermore, two specific starch dicarboxylic acid derivatives, i.e. G and F having a 22% and 45% degree of carboxylation also exhibited outstanding builder properties in a detergent formulation.

The three specific formulations discussed above all were either equivalent or superior in performance to their phosphorous containing analog.

During the formulation and testing of the partially dicarboxylated starches (G) and (F) it was found that in alkaline medium the detergent turned into an amber colored material which may have been due to the degradation of the starch dialdehyde present. When the partially dicarboxylated starch was formulated in acidic solution, no darkening was noted. Hence, this material was evaluated at two different pH values6.0 and 10.0 (acid and alkaline). It was found that the effect of lower pH resulted in very serious degradation in building action. This effect is much more pronounced than that caused by the aldol condensation. Hence, a serious decline in detergency rules out any possibility of using the partially dicarboxylated starches at lower pHs.

A detergent grade carboxymethyl cellulose (sodium salt) which had a degree of substitution of 0.7 out of a maximum possible 3.0 was evaluated for detergency building action. At present, this material is widely used in low concentrations of about 1% as an anti-redeposition agent l 8 EXAMPLE 3 This example relates to heavy duty liquid laundry detergents as opposed to light duty liquid dishwashing and hand laundry formulations.

Tetrapotassium pyrophosphate (TKPP) is the typical builder used in todays liquid laundry detergents. It has a relatively low chelation value mgm. CaCO per gram) but is used because of its superior solubility over other types of phosphate builders, i.e. STPP. Very often hydrotropes are required to solubilize higher concentrations of TKPP.

Starch derivatives were evaluated in this example as potential replacements for TKPP in the belief that they will be more soluble and be able to form clear solutions without the use of hydrotropes such as sodium xylene sulfonate. In test formulations prepared to replace TKPP by starch and starch derivatives, no hydrotropes were required.

A series of detergency tests exactly similar to the detergency test procedures described in Example 2 was carried out on liquid laundry formulations,

These liquid laundry compositions had the following formulations:

Percent by wt. Surfactant linear alkyl C (average) benzene sulfonate 15 Sodium metal silicate 5 Builder 15 Water Balance Formulations according to the above were made up using as builders the carboxymethyl starches used in Example 2. The results obtained with the 18% substituted carboxymethyl starch were outstanding and are summarized below in Table IV.

The other starch derivatives did not make satisfactory liquid detergent formulations.

TABLE IV.SIMILAR TO TABLE III BUT DIRECTED TO HEAVY DUTY LIQUID DETERGENT FORMULATIONS Percent reflectance at different builder concentrations Percent carbox- 0.01% 0.02% 0.03% 0.06% 0.09% 0.12% Material tested ylation Builder Builder Builder Builder Builder Builder Carboxymethyl starch l 18 2 41. 0 3 42. 0 4 44. 0 c. 49. 4 KPP 33. 5 41.0 47.5 44. 3

1 From National Starch and Chemical Corporation (1.34 degree of substitution). 2 Taken at 0.025% builder concentration. 3 Taken at 0.050% builder concentration. 4 Taken at 0.075% builder concentration.

5 Taken at 0.15%.

in household laundry detergents. The sodium-CMC has a positive detergency building action, although it did not perform as well as STPP. It did perform better than some of the carboxy containing starches. Other data indicated that the chelation ability of CMC decreased with increases in temperature. It would therefore be suggested to explore the possibility of using CMC in cold water formulations. Also, it suggests exploring the use of CMC as a detergent builder, which has higher degrees of substitution than 0.7, such as 1.0, 1.5, 2.5 and 3.0.

Starch dialdehydes which are starches which have substituted aldehyde units thereon were tested. Starch dialdehyde had a very low chelation power, i.e. 8.5 mg. CaCO per gram, and as expected had a very poor detergency building action. There is even a decline in overall detergency with increase in starch dialdehyde content. In fact, the maximum detergency was obtained at zero percent starch dialdehyde concentration.

Moreover, other data obtained (which is not shown in Table IV) demonstrates that the other starch derivatives tested are so inferior in detergency that they will not be able to compete with TKPP even with their lack of eutrophication difficulties. Starch dialdehydes are even more deficient.

Thus, a certain carboxymethyl starch having specified properties has been shown to be the best detergent builder of all starch derivatives tested in liquid and solid heavy duty formulations.

CMC was almost equivalent to sodium tripolyphosphate in solid laundry detergents. On the basis of detergency alone, CMC offers a possible challenge to all phosphate builders in all types of aundry situations.

EXAMPLE 4 The procedure of Example 2 was repeated exactly except for the difference in the type of cloth used with one additional sample of starch dicarboxylic acid salt and two additional samples of carboxymethyl starch salts. The results are summarized in Tables V and VI as follows:

TABLE V.DETERGENCY BUILDING POWER OF STARCII DICARBOXYLIC ACID USED TO WASH SOILED COTTON PREPARED BY AMERICAN CONDITIONING IIOUSE COMPANY Percent reflectance at different builder concentration Percent carboxy- 0. 00% 0- 09% Material tested lation builder builder builder Starch dicarboxylic acid (I'I) 40. 6 30. 0 40. 41. 5 Sodium tripolyphosphate 30. 6 41. 5

TABLE VI.DETERGENCY BUILDING POWER OF CARBOXYMETIIYL STARCHES PREPARED BY THE SOLUTION METHOD \ND USED TO \VASH SOILED CATION PREPARED BY AMERICAN CONDITIONING HOUSE COMPANY Material tested Description Percent reflectance at ditlerent builders concentration Percent carboxy- 0 0. 06% 0. 09% Name lation D.S. builder builder builder Carboxymcthyl starch. 26. 8 2 30. 5 D 26. 8 2 30.5

As can be seen from the above tables none of the samples were quite effective as STPP, but they were in the same order of magnitude of effectiveness. They will make effective commercial replacements for STPP.

While the preferred starch derivatives described herein are excellent detergent builders in and of themselves they can also be used in combination with other builders. These other builders include those known to the art such as the phosphates, aminocarboxylates (e.g. SNTA) and those discovered and invented by the inventor herein such as citrates and polyacrylates.

The quantities and amounts can be adjusted so that the desired advantageousness of the combinations will be maximized and the weaknesses will be minimized.

What is claimed is:

1. A cleansing and laundering composition consisting essentially of (a) an organic water-soluble detergent surfactant selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic detergent surfactants, and mixtures thereof;

(b) a starch derivative salt present in builder quantities prepared from a solution process or a granular process plus subsequent degradation characterized by not showing the characteristic blue color when reacted with iodine selected from the group consisting of:

(1) starch dicarboxylic acid salts having a carboxylic acid content of about to 47%, a molecular weight (Weight average) of about 200,000 to 1,000,000 and a carboxy degree of substitution of about 0.5 to 2.0;

(2) carboxymethyl starch salts having a carboxy acid group content of from about 10 to 40.2%, a carboxy degree of substitution of about 0.5 to 2.5 and a molecular Weight (weight average) of about 200,000 to 1,000,000; and wherein the ratio of said starch derivative builder to said detergent surfactant is in the range of from 1:5 to 10:1 by weight.

2. A composition according to claim 1 wherein said composition exhibits the physical/chemical property of being able to chelate at least 40 mgm. of CaCO per gram of active builder material.

3. The composition of claim 1 which is a heavy duty solid.

8. The composition according to claim 1 wherein said repeating monomer unit is and n is a number from 1,000 to 5,000 and M is sodium, potassium or ammonium radicals.

9. The composition according to claim 1 wherein each repeating monomer unit is CH OH OM II l/ LO 0 C (H) (H) n and n is a number from 1,000 to 5,000 and M is sodium, potassium or ammonium radical.

10. The composition according to claim 1 wherein there is a random distribution of any or all of the following monomer units:

0 T 11 OM 0M I 0 C 0 H H O O x starch dicarboxylato ([lHzOll o II H II I l (|)M Til C C II II U U --y starch monocarboxylatc OHQOH OCHZOOOM H I H CH2 011,011 I I 11 I- H H I H i H 5 l H K C OCH COOM H OHH l L L ll T Z H oofi oooM y H on 2 starch dialdehyde and X, Y and Z are numbers from 1,000 to 5,000 and M is sodium, potassium or ammonium radical.

11. The composition according to claim 1 wherein and w, x, y and z are numbers from 1,000 to 5,000 each monomer repeating unit is:

and M is a sodium, potassium or ammonium radical.

(RCHZCOOM 13. A composition according to claim 1 wherein said on, carboxymethyl starch has a degree of substitution of I 0 carboxy groups of from 1 to 1.5. 14. A composition according to claim 1 wherein the I molecular Weight of said starch derivatives is from OH H/ 500,000 to 800,000 weight average.

I- I J 15. A composition according to claim 1 wherein said H OH 11 starch derivatives are mildly degraded products from a or granular starch derivative.

16. An aqueous washing solution containing from about (ICHZCOOM .01 to 50 wt. percent of the builder of claim 1. GHQ 17. An aqueous washing solution according to claim I 0 16 which has a pH range of from about 9.5 to 11.5. H H H I References Cited OCHZCOOM o- UNITED STATES PATENTS L I L I 2,588,463 3/1952 Balassa 260-233.3 2,847,385 8/1958 Hiler 25289 lsomers 1S a {lumber from 12000 2,894,945 7/1959 Hofreiter et al. 260-2333 to 5,000 and M is sodium, potassium or ammonium 3,062,810 11/1962 Hjermstad et aL 252 89 radlcal- 3,335,086 8/1967 Morris 252 s9 12. The composition according to claim 1 wherein there is a random distribution of any or all of the LEON DROSDOLPrimary Examiner following monomer units or of their isomers:

W. E. SCHULZ, Asslstant Examiner OCHQCOOM OCHQCOOM 4 (5H, 0'11. 0 US. 01. X. R. H([ H H H 252132,135,137,138,142,152,161 I \OHH I ooinoooivr H L '1L' 'l H 0 .1 w H OH x 

